TWI434965B - A roughening method for copper foil, and a copper foil for a printed wiring board which is obtained by the roughening method - Google Patents
A roughening method for copper foil, and a copper foil for a printed wiring board which is obtained by the roughening method Download PDFInfo
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- TWI434965B TWI434965B TW098117407A TW98117407A TWI434965B TW I434965 B TWI434965 B TW I434965B TW 098117407 A TW098117407 A TW 098117407A TW 98117407 A TW98117407 A TW 98117407A TW I434965 B TWI434965 B TW I434965B
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- Prior art keywords
- copper
- copper foil
- printed wiring
- wiring board
- fine
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 311
- 239000011889 copper foil Substances 0.000 title claims description 148
- 238000007788 roughening Methods 0.000 title claims description 59
- 238000000034 method Methods 0.000 title claims description 44
- 229910052802 copper Inorganic materials 0.000 claims description 163
- 239000010949 copper Substances 0.000 claims description 163
- 239000002245 particle Substances 0.000 claims description 67
- 238000007747 plating Methods 0.000 claims description 57
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 54
- 229920000642 polymer Polymers 0.000 claims description 43
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 239000000758 substrate Substances 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 19
- 238000005868 electrolysis reaction Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 12
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical group C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 2
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 17
- 230000003746 surface roughness Effects 0.000 description 17
- 238000001556 precipitation Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 9
- 229920000106 Liquid crystal polymer Polymers 0.000 description 8
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 8
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 230000002411 adverse Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920005992 thermoplastic resin Polymers 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- -1 halogen ions Chemical class 0.000 description 5
- 229920006380 polyphenylene oxide Polymers 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241001424392 Lucia limbaria Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/03—Metal processing
- H05K2203/0307—Providing micro- or nanometer scale roughness on a metal surface, e.g. by plating of nodules or dendrites
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/0723—Electroplating, e.g. finish plating
Description
本案發明是關於銅箔之粗化處理方法以及此粗化處理方法所獲致之印刷配線板用銅箔。更詳細而言是有關於一種銅箔之粗化方法、此粗化處理方法所獲致之印刷配線板用銅箔、使用此印刷配線板用銅箔所獲致之覆銅積層板、使用此覆銅積層板所獲致之印刷配線板。特別是有關於適於形成細微間距的配線電路的印刷配線板用銅箔之粗化處理方法。The present invention relates to a copper foil roughening treatment method and a copper foil for a printed wiring board obtained by the roughening treatment method. More specifically, it relates to a method for roughening a copper foil, a copper foil for a printed wiring board obtained by the roughening treatment method, a copper-clad laminate obtained by using the copper foil for the printed wiring board, and using the copper-clad laminate A printed wiring board obtained by a laminate. In particular, there is a method of roughening a copper foil for a printed wiring board suitable for forming a wiring circuit having a fine pitch.
因應對於電子機器的小型化、輕量化等的所謂輕薄短小化的要求，近年的印刷配線板亦被進行同樣的要求。然後，由於搭載此些電子機器的資訊處理工具的高性能化，操作訊號的時脈頻率超過10GHz亦變為一般化。亦即是，用以製造印刷配線板的覆銅積層板中，被要求採用低介電常數的絕緣樹脂基材。對應此種小型輕量化的電子機器中，多見採用形成有細微間距的配線電路的可撓式印刷配線板的例子。而且，封裝積體電路(Integrated Circuit,IC)或大型積體電路(Large Scale Integration,LSI)的封裝基板，亦多採用作為可撓式印刷配線板的捲帶式封裝(Tape Carrier Package,TCP)。In recent years, printed wiring boards have been subjected to the same requirements in response to demands for so-called thinness and lightness, such as miniaturization and weight reduction of electronic equipment. Then, due to the high performance of information processing tools equipped with such electronic devices, the clock frequency of the operation signals exceeding 10 GHz has become generalized. That is, in the copper clad laminate for manufacturing a printed wiring board, an insulating resin substrate having a low dielectric constant is required. In an electronic device that is small and lightweight, an example of a flexible printed wiring board in which a wiring circuit having a fine pitch is formed is often used. Moreover, a package substrate including an integrated circuit (IC) or a large scale integrated circuit (LSI) is also used as a tape carrier package (TCP) as a flexible printed wiring board. .
然後，低介電常數的絕緣樹脂材料，以熱塑性樹脂的聚苯醚(Polyphenylene Ether,PPE)、聚苯醚(Polyphenylene Oxide,PPO)、氟樹脂或液晶聚合物作為代表的樹脂。但是，此些樹脂難以安定的發揮與印刷配線板用銅箔的良好接著力。其中當使用熱塑性樹脂作為基材使用時，此種的接著不安定化的傾向特別是顯著的呈現。Then, the low dielectric constant insulating resin material is represented by a thermoplastic resin such as polyphenylene oxide (PPE), polyphenylene oxide (PPO), fluororesin or liquid crystal polymer. However, such resins are difficult to stably exhibit good adhesion to the copper foil for printed wiring boards. Among them, when a thermoplastic resin is used as a substrate, such a tendency to be unstable is particularly remarkable.
此處，明確的論及發揮銅箔與樹脂的接著力的機制，可說是由化學接著力與物理接著力的總和力來決定接著力的等級。由此機制來看，與銅箔層合的絕緣樹脂層使用熱固性樹脂時，在銅箔的表面形成矽烷偶合劑層並與樹脂的硬化反應匹配，藉此容易使化學接著力安定化。但是，如果與銅箔層合的絕緣樹脂層使用熱塑性樹脂時，由於無法大的期待上述的化學接著力的安定化，為了得到與銅箔的安定接著力，對銅箔施加粗化處理，而藉由錨效果引出接著力的物理接著力是重要的。Here, a clear discussion of the mechanism for exerting the adhesion between the copper foil and the resin can be said to determine the level of the adhesion force by the sum of the chemical adhesion force and the physical adhesion force. According to this mechanism, when a thermosetting resin is used as the insulating resin layer laminated with the copper foil, a decane coupling agent layer is formed on the surface of the copper foil to match the curing reaction of the resin, whereby the chemical adhesion is easily stabilized. However, when a thermoplastic resin is used for the insulating resin layer laminated with the copper foil, since the above-mentioned chemical adhesion force stability cannot be expected, the copper foil is roughened in order to obtain a stable adhesion force with the copper foil. It is important to derive the physical adhesion of the force by the anchor effect.
此處，請參照專利文獻1(國際申請：WO2003/102277號公報)，其目的在提供一種表面處理銅箔，能夠充分的確保與構成高頻用途的印刷配線板時所使用的低介電性基材的接著強度，並能夠極力抑制傳送損失，而揭示一種用以接著於低介電常數基材的低介電常數基材用表面處理銅箔。更具體來說，其揭示在銅箔表面形成瘤狀銅粒所構成的粗化處理層，並於該粗化處理層的表面全體析出附著極細微銅粒子，當該表面粗度值Rz為1.0～6.5μm，且為當該表面處理銅箔的表面色L*為50以下、a*為20以下、b*為15以下的表面處理銅箔。然後，在該粗化處理層的瘤狀銅粒表面全體形成細微銅粒子的表面上，具備含有鋅、鎳的至少一種的防鏽處理層。然後，依照實施例，對於熱固性PPO，使用標稱厚度12μm(表面粗度Rz 3.5μm)、以及35μm(表面粗度Rz 4.6μm)的電解銅箔進行層合，12μm厚的銅箔得到0.72kN/m、35μm厚的銅箔得到1.00kN/m的剝離強度。In the case of the surface-treated copper foil, it is possible to sufficiently ensure the low dielectric property used when forming a printed wiring board for high-frequency use. The adhesion strength of the substrate and the transmission loss can be suppressed as much as possible, and a surface-treated copper foil for a low dielectric constant substrate which is followed by a low dielectric constant substrate is disclosed. More specifically, it discloses a roughened layer formed by forming a knob-like copper particle on the surface of the copper foil, and deposits fine fine copper particles on the surface of the roughened layer, when the surface roughness value Rz is 1.0. ～6.5 μm is a surface-treated copper foil having a surface color L* of 50 or less, a* of 20 or less, and b* of 15 or less in the surface-treated copper foil. Then, at least one type of rust-preventing treatment layer containing zinc or nickel is provided on the surface of the entire surface of the knob-shaped copper particles of the roughened layer to form fine copper particles. Then, according to the examples, for the thermosetting PPO, lamination was performed using an electrolytic copper foil having a nominal thickness of 12 μm (surface roughness Rz 3.5 μm) and 35 μm (surface roughness Rz 4.6 μm), and a 12 μm thick copper foil was obtained by 0.72 kN. The /m, 35 μm thick copper foil gave a peel strength of 1.00 kN/m.
而且，專利文獻2(日本專利申請：特開2005-248323號公報)中揭露一種表面處理銅箔，可作為吸濕性低、銅箔與具有優良耐熱性的液晶聚合物膜層合、與絕緣樹脂基材的接著強度大、且能夠細微間距的配線電路化的基板用複合材料。此處所謂的表面處理銅箔，記載了在附著粗化粒子以作為粗化面的銅箔，其具備表面粗糙度Rz為1.5～4.0μm，亮度為30以下的粗化處理面的表面處理銅箔，較佳為由粗化粒子形成的突起物的高度為1μm～5μm，觀察斷面25μm的範圍以6～35個的個數略均等的分佈，而且較佳各突起物的最大寬度為0.01μm以上、在25μm範圍內存在的突起物個數除以25μm的長度的2倍以下。然後，依照專利文獻2的實施例，表面粗度Rz為2.5μm～3.7μm、亮度16～23的12μm電解銅箔與液晶聚合物膜進行層合，得到0.55kN/m～1.31kN/m的剝離強度。Further, a surface-treated copper foil which is low in hygroscopicity, copper foil and liquid crystal polymer film having excellent heat resistance is laminated and insulated as disclosed in Japanese Laid-Open Patent Publication No. 2005-248323. A composite material for a substrate having a large bonding strength of a resin substrate and capable of wiring at a fine pitch. In the surface-treated copper foil, a copper foil having a roughened surface to which roughened particles are attached is provided, and a surface-treated copper having a roughened surface having a surface roughness Rz of 1.5 to 4.0 μm and a luminance of 30 or less is provided. Preferably, the foil has a height of 1 μm to 5 μm from the roughened particles, and a range of 25 μm in the observation section is slightly equal to 6 to 35, and preferably the maximum width of each of the protrusions is 0.01. The number of protrusions existing in the range of μm or more and 25 μm is divided by two times or less the length of 25 μm. Then, according to the embodiment of Patent Document 2, a 12 μm electrolytic copper foil having a surface roughness Rz of 2.5 μm to 3.7 μm and a luminance of 16 to 23 is laminated with a liquid crystal polymer film to obtain 0.55 kN/m to 1.31 kN/m. Peel strength.
但是，如同上述專利文獻2中所記載，作為提升絕緣樹脂基材與銅箔的密著性，如將與絕緣樹脂基材接著的銅箔之粗化處理面的粗糙度變大，則具有接著強度變大的傾向，但是另一方面通常會產生難以形成細微間距的配線電路的缺點。例如是請參照專利文獻2的比較例7，此處所使用銅箔的與絕緣樹脂基材的層合面的表面粗糙度Rz為3.65μm，由於具備大的粗糙度而使得銅箔與絕緣樹脂基材的接著強度(剝離強度)大。但是，以減成法形成的配線電路，線/空間為55μm/55μm(110μm間距)成為界限。同樣的，即使參照專利文獻2的實施例2，由於使用具備與比較例7同等級表面粗糙度的銅箔，可理解形成50μm/50μm(100μm間距)的配線電路成為界限。而且，可理解如要形成25μm/25μm(50μm間距)的配線電路，則必須使用表面粗糙度Rz為2.5μm以下的銅箔。However, as described in the above-mentioned Patent Document 2, as the adhesion between the insulating resin substrate and the copper foil is increased, the roughness of the roughened surface of the copper foil which is next to the insulating resin substrate is increased. The strength tends to increase, but on the other hand, there is usually a disadvantage that it is difficult to form a fine pitch wiring circuit. For example, referring to Comparative Example 7 of Patent Document 2, the surface roughness Rz of the laminated surface of the copper foil and the insulating resin substrate used herein is 3.65 μm, and the copper foil and the insulating resin base are provided because of having a large roughness. The material has a large adhesive strength (peel strength). However, the wiring circuit formed by the subtractive method has a line/space of 55 μm/55 μm (110 μm pitch). In the same manner, in the second embodiment of Patent Document 2, since a copper foil having the same surface roughness as that of Comparative Example 7 was used, it was understood that a wiring circuit having a thickness of 50 μm/50 μm (100 μm pitch) was defined. Further, it is understood that if a wiring circuit of 25 μm / 25 μm (50 μm pitch) is to be formed, it is necessary to use a copper foil having a surface roughness Rz of 2.5 μm or less.
此處參照上述專利文獻1以及專利文獻2的揭示內容來看可製造的銅箔之粗化處理面的表面粗糙度，專利文獻1的表面粗度值Rz為1.0～6.5μm，專利文獻2的表面粗度值Rz為1.5～4.0μm。亦即是，專利文獻1的銅箔的輪廓(profile)分類為IPC規格的Type-V～Type-L，專利文獻2的銅箔的輪廓分類為IPC規格的Type-V，而含有非一般印刷配線板用銅箔，係屬於低輪廓銅箔的範疇。With reference to the disclosures of Patent Document 1 and Patent Document 2, the surface roughness of the roughened surface of the copper foil which can be produced, the surface roughness value Rz of Patent Document 1 is 1.0 to 6.5 μm, and Patent Document 2 The surface roughness value Rz is 1.5 to 4.0 μm. In other words, the profile of the copper foil of Patent Document 1 is classified into Type-V to Type-L of the IPC standard, and the outline of the copper foil of Patent Document 2 is classified into Type-V of the IPC specification, and contains non-general printing. Copper foil for wiring boards is a category of low profile copper foil.
但是，將絕緣層使用液晶高分子的印刷配線板作為封裝LSI等的TCP、薄膜覆晶封裝(Chip on Film,COF)等使用時的配線電路，一般要求50μm以下的電路間距。於此情況，上述專利文獻1或專利文獻2所揭示的技術無法安定的作成所需電路間距，因此要求具備能夠形成50μm以下的電路間距的細微間距配線電路的粗化處理面的銅箔。However, a printed wiring board using a liquid crystal polymer as an insulating layer is used as a wiring circuit for use in a TCP or a film on-chip (COF) such as a package LSI, and a circuit pitch of 50 μm or less is generally required. In this case, the technique disclosed in Patent Document 1 or Patent Document 2 cannot provide a desired circuit pitch, and therefore, it is required to include a copper foil having a roughened surface of a fine pitch wiring circuit capable of forming a circuit pitch of 50 μm or less.
此處本案發明者們銳意研究的結果，想到了以下所示的可形成細微間距的配線電路的印刷電路板用銅箔之粗化處理方法、使用此粗化處理方法所獲致之印刷配線板用銅箔、使用此印刷配線板用銅箔的覆銅積層板以及使用此覆銅積層板的印刷配線板。As a result of intensive research by the inventors of the present invention, a method of roughening a copper foil for a printed circuit board which can form a wiring circuit having a fine pitch as described below, and a printed wiring board obtained by using the roughening method are conceivable. A copper foil, a copper-clad laminate using the copper foil for printed wiring boards, and a printed wiring board using the copper-clad laminate.
本案發明的銅箔之粗化處理方法：本案發明的銅箔之粗化處理方法，是將銅箔的與絕緣樹脂基材的層合面粗化，其使用含有四級銨鹽聚合物的硫酸系鍍銅液，以於銅箔表面析出形成細微銅粒子。The copper foil roughening treatment method according to the present invention is a method for roughening a copper foil according to the present invention, in which a copper foil and a laminated surface of an insulating resin substrate are coarsened, and a sulfuric acid containing a quaternary ammonium salt polymer is used. A copper plating solution is formed to precipitate fine copper particles on the surface of the copper foil.
本案發明的印刷配線板用銅箔：使用上述粗化處理方法而形成有粗化處理面的銅箔，其粗化處理均勻且緻密，因此適用於印刷配線板用銅箔。The copper foil for a printed wiring board according to the present invention is a copper foil having a roughened surface formed by the above-described roughening treatment method, and the roughening treatment is uniform and compact, and therefore is suitable for a copper foil for a printed wiring board.
本案發明的覆銅積層板：本案發明的覆銅積層板，其特徵在於：使用藉由上述粗化處理方法形成有粗化處理面的銅箔，與絕緣樹脂基材層合而得到的。The copper-clad laminate according to the present invention is characterized in that the copper-clad laminate according to the present invention is obtained by laminating a copper foil having a roughened surface formed by the above-described roughening treatment method, and an insulating resin substrate.
本案發明的印刷配線板：本案發明的印刷配線板，其特徵在於：對上述覆銅積層板施行蝕刻等的二次加工而得到的。The printed wiring board according to the invention of the present invention is characterized in that the copper clad laminate is subjected to secondary processing such as etching.
本案發明的銅箔之粗化處理方法，是將銅箔的與絕緣樹脂基材的層合面粗化的方法，使用特定的硫酸系鍍銅液而在銅箔表面析出形成細微銅粒子。藉由使用此粗化處理方法，而能夠在銅箔的表面施加緻密且均勻的粗化處理。此種具備粗化處理面的銅箔適於作為印刷配線板用銅箔。亦即是，具備依本案發明的粗化處理方法粗化的粗化處理面的銅箔，其粗化處理面用作為與絕緣樹脂基材的接著面，藉此顯示了與具備低介電損失特性的熱塑性樹脂構成的絕緣樹脂基材的良好密著性，而適於製造具備適於形成細微間距的配線電路的粗化處理面的印刷配線板。The method for roughening the copper foil according to the present invention is a method of roughening the laminated surface of the copper foil and the insulating resin substrate, and depositing fine copper particles on the surface of the copper foil by using a specific sulfuric acid-based copper plating solution. By using this roughening treatment method, a dense and uniform roughening treatment can be applied to the surface of the copper foil. Such a copper foil having a roughened surface is suitable as a copper foil for a printed wiring board. In other words, the copper foil having the roughened surface which is roughened by the roughening treatment method according to the present invention has a roughened surface as a contact surface with the insulating resin substrate, thereby exhibiting a low dielectric loss. The insulating resin substrate made of a thermoplastic resin having properties is excellent in adhesion, and is suitable for producing a printed wiring board having a roughened surface suitable for forming a wiring circuit having a fine pitch.
為了使本案發明的銅箔之粗化處理方法更容易理解，對於印刷配線板用電解銅箔的一般製造方法進行確認。尚且，本案發明單純稱為「銅箔」的情況，是記載為包含電解銅箔、壓延銅箔、附載體銅箔的全部概念。In order to make the copper foil roughening treatment method of the present invention easier to understand, the general production method of the electrolytic copper foil for printed wiring boards was confirmed. In addition, the case where the invention of the present invention is simply referred to as "copper foil" is described as including the electrolytic copper foil, the rolled copper foil, and the copper foil with a carrier.
首先簡單描述電解銅箔的製程。對於電解銅箔的情況，在旋轉陰極上電附著銅，已電附著的銅呈箔狀，而開始此些的捲取並採收。於此階段由於未施加任何表面處理而有時亦稱為「未處理電解銅箔」。其後，當該電解銅箔在其表面因應粗化處理或防鏽處理等的要求品質而施加表面處理，進而成為作為製品的電解銅箔。因此，市面上稱為「電解銅箔」者，嚴格來說是表面經處理的「表面處理電解銅箔」。First, the process of electrolytic copper foil will be briefly described. In the case of an electrolytic copper foil, copper is electrically attached to the rotating cathode, and the copper which has been electrically adhered is in the form of a foil, and the winding is started and recovered. At this stage, it is sometimes referred to as "untreated electrolytic copper foil" because no surface treatment is applied. Then, the electrodeposited copper foil is subjected to surface treatment in accordance with the required quality such as roughening treatment or rust-preventing treatment, and further becomes an electrolytic copper foil as a product. Therefore, it is called "electrolytic copper foil" on the market, and it is strictly a surface treated electrolytic copper foil.
而且，對於壓延銅箔的情況，考慮到最終的用途而調製成分經過調整的銅錠，由此銅錠反覆進行壓延加工與熱處理，而得到特定厚度的銅箔。對於壓延銅箔的情況，由於未施加任何表面處理而有時亦稱為「未處理電解銅箔」。其後，當該壓延銅箔與電解銅箔的情況相同，在其表面因應粗化處理或防鏽處理等的要求品質而施加表面處理，進而成為作為製品的壓延銅箔。因此，市面上稱為「壓延銅箔」者，嚴格來說是表面經處理的「表面處理壓延銅箔」。Further, in the case of rolling the copper foil, the copper ingot having the adjusted composition is prepared in consideration of the final use, whereby the copper ingot is subjected to rolling processing and heat treatment in reverse to obtain a copper foil having a specific thickness. In the case of rolling a copper foil, it is sometimes referred to as "untreated electrolytic copper foil" because no surface treatment is applied. Then, in the same manner as in the case of the electrodeposited copper foil, the surface of the rolled copper foil is subjected to surface treatment in accordance with the required quality such as roughening treatment or rust-preventing treatment, and further becomes a rolled copper foil as a product. Therefore, those who are called "rolled copper foil" on the market are strictly "surface-treated rolled copper foil" which has been treated on the surface.
本案發明的銅箔之粗化處理方法，是粗化銅箔的與絕緣樹脂基材的層合面的方法。然後，以下詳細說明此粗化處理方法。The method for roughening the copper foil according to the present invention is a method of roughening the laminated surface of the copper foil and the insulating resin substrate. Then, the roughening processing method will be described in detail below.
本案發明的銅箔之粗化處理方法，基本上是使用含有四級銨鹽聚合物的硫酸系鍍銅液，以燒鍍銅條件電解，並於銅箔表面析出形成細微銅粒子。如同專利文獻2所揭示，一般的方法是採用在電解銅箔的具有凹凸的析出面側析出形成銅粗化粒子的方法。這是因為在凹凸的頂部產生電流集中而容易燒鍍銅。相對於此，本案發明的粗化處理，藉由使用含有四級銨鹽聚合物的硫酸系鍍銅液，即使是在具備無凹凸平坦表面的電解銅箔、壓延銅箔的表面上亦能夠析出均勻且細微的銅粒子。亦即是，使用特定硫酸銅系鍍銅液，對液溫與電流密度作最適當的設定，藉此燒鍍銅狀態的細微銅粒子即使是平坦的表面亦能夠均勻且細微的析出。The copper foil roughening treatment method of the present invention basically uses a sulfuric acid-based copper plating solution containing a quaternary ammonium salt polymer, and is electrolyzed by a copper plating condition to precipitate fine copper particles on the surface of the copper foil. As disclosed in Patent Document 2, a general method is a method in which copper roughened particles are deposited on the side of the deposition surface of the electrolytic copper foil having irregularities. This is because current concentration is generated at the top of the unevenness and it is easy to burn copper. On the other hand, in the roughening treatment of the present invention, by using a sulfuric acid-based copper plating solution containing a quaternary ammonium salt polymer, it is possible to precipitate even on the surface of an electrolytic copper foil or a rolled copper foil having a flat surface without unevenness. Uniform and fine copper particles. In other words, by using a specific copper sulfate-based copper plating solution, the liquid temperature and the current density are optimally set, whereby the fine copper particles in the copper-plated state can be uniformly and finely precipitated even on a flat surface.
描述關於本案發明的銅箔之粗化處理方法所使用的硫酸系鍍銅液。本案發明所使用的硫酸系鍍銅液，含有四級銨鹽聚合物。藉由使用此四級銨鹽聚合物，即使是作為陰極的未處理銅箔的表面僅具備微米等級凹凸而無電流集中部位時，亦能夠在其表面均勻的析出細微銅粒子，且在同一面所析出的細微銅粒子並沒有偏移存在的情形。亦即是，以燒鍍銅條件析出形成的細微銅粒子的形狀、銅粒子尺寸的散亂小，且能夠安定的析出形成較佳的細微銅粒子。而且，上述的四級銨鹽聚合物由於在硫酸系鍍銅液中的添加量少就足夠，雖然是吸附在銅上的成分，但是由於在析出的細微銅粒子中混入的不純物少，對於所獲致之銅箔的導電性能不會產生不良影響。A sulfuric acid-based copper plating solution used in the method for roughening copper foil of the present invention will be described. The sulfuric acid-based copper plating solution used in the invention of the present invention contains a quaternary ammonium salt polymer. By using the quaternary ammonium salt polymer, even when the surface of the untreated copper foil as the cathode has only micron-order irregularities and no current concentration portion, fine copper particles can be uniformly deposited on the surface thereof, and on the same side. The precipitated fine copper particles are not offset. In other words, the shape of the fine copper particles deposited by the copper plating conditions and the small size of the copper particles are small, and the fine copper particles can be formed by stable precipitation. Further, the above-described quaternary ammonium salt polymer is sufficient because the amount of addition to the sulfuric acid-based copper plating solution is small, and although it is a component adsorbed on copper, the amount of impurities mixed in the precipitated fine copper particles is small. The conductive properties of the obtained copper foil do not adversely affect.
而且，作為添加劑的四級銨鹽聚合物，由減輕排水處理負荷的觀點來看亦是適當的。例如是專利文獻1提出使用金屬鹽作為添加劑，添加被認為具有使粗化銅粒子的析出狀態安定化效果的砷(As)以析出硬銅合金粒子。但是此As的使用對排水處理的負荷變大而導致製造管理成本的增加，由可能對人體產生直接的不良影響來看As的使用是需避免的。因此，作為排水負荷少、對人體影響少、可安定燒鍍銅的添加劑，選擇使用四級銨鹽聚合物。Further, the quaternary ammonium salt polymer as an additive is also suitable from the viewpoint of reducing the drainage treatment load. For example, Patent Document 1 proposes to use arsenic (As) which is considered to have an effect of stabilizing the precipitation state of roughened copper particles by using a metal salt as an additive to precipitate hard copper alloy particles. However, the use of this As increases the load on the drainage process and leads to an increase in the cost of manufacturing management. The use of As is to be avoided by the direct adverse effects that may be caused to the human body. Therefore, as an additive having a small drainage load and having little influence on the human body and capable of stably baking copper, a quaternary ammonium salt polymer is selected.
於此四級銨鹽聚合物中，如具備有聚合物所具備的直鏈部分為烴所構成的化學結構，能更安定的發揮效果。此處所謂的四級銨鹽聚合物可使用具備直鏈結構或環狀結構的任一者。於直鏈結構的四級銨鹽聚合物時，較佳是於主鏈含有四級銨鹽結構。而且，於具有環狀結構的四級銨鹽聚合物時，較佳使用具有2聚體以上的環狀結構的二烯丙基二甲基氯化銨聚合物。二烯丙基二甲基氯化銨聚合物在構成聚合物時形成環狀結構，此環狀結構的一部份由四級銨鹽的氮原子所構成。但是，具有環狀結構的二烯丙基二甲基氯化銨聚合物中，前述環狀結構為5員環或6員環等以複數型態存在。實際的聚合物則是根據聚合條件來考量此些的任一或是混合物的構成。此處，以下是以此些聚合物內為5員環的化合物為代表例，且具備氯離子作為對離子者表示於化學式1。In the quaternary ammonium salt polymer, if the linear structure of the polymer is a hydrocarbon, the chemical structure can be more stable. The quaternary ammonium salt polymer referred to herein may be any one having a linear structure or a cyclic structure. In the case of a linear quaternary ammonium salt polymer, it is preferred to have a quaternary ammonium salt structure in the main chain. Further, in the case of a quaternary ammonium salt polymer having a cyclic structure, a diallyldimethylammonium chloride polymer having a cyclic structure of a dimer or more is preferably used. The diallyldimethylammonium chloride polymer forms a cyclic structure when constituting the polymer, and a part of the cyclic structure is composed of a nitrogen atom of a quaternary ammonium salt. However, in the diallyldimethylammonium chloride polymer having a cyclic structure, the cyclic structure is a 5-membered ring or a 6-membered ring or the like in a plural form. The actual polymer is considered to be any one of these or a mixture depending on the polymerization conditions. Here, the following is a representative example of a compound having a 5-membered ring in the polymer, and a chlorine ion as a counter ion is represented by Chemical Formula 1.
然後，本案發明的銅箔之粗化處理方法中所使用的「含有四級銨鹽聚合物的硫酸系鍍銅液」中，較佳將鹵離子控制於一定的範圍內。鹵離子如同前述的具備吸附於銅的性質，條件共通的話，依照碘離子、溴離子、氯離子、氟離子的順序而多吸附。但是由操作容易性與以硫酸根含量多的鍍銅液為對象的平衡來考慮的話，使用氯離子會成為最為穩定的吸附狀態。以下描述限定為氯離子。In the "sulfuric acid-based copper plating solution containing a quaternary ammonium salt polymer" used in the copper foil roughening method of the present invention, it is preferred to control the halogen ions within a certain range. The halide ion has the property of being adsorbed to copper as described above, and if it is common, it is adsorbed in the order of iodide ion, bromide ion, chloride ion, and fluoride ion. However, considering the ease of handling and the balance of the copper plating solution having a large sulfate content, the use of chloride ions is the most stable adsorption state. The following description is defined as chloride ions.
此處所述的硫酸系鍍銅液中的氯離子，於鍍銅步驟中由於具有吸附於析出的金屬銅的表面，並提升表面狀態的均勻性的效果，較佳併用有機系的添加劑。然後，藉由併用四級銨鹽聚合物與氯離子，氯離子吸附於銅，並發揮適度的抑制對銅表面的銅電附著的效果。因此，在得到表面平滑的鍍銅層的情況下，多嘗試氯離子的控制。藉由此種的使四級銨鹽聚合物與氯離子於溶液中並存，對銅箔表面吸附的氯離子，伴隨著表面電位的變化而於析出表面上移動，其中表面電位的變化是伴隨著銅粒子的析出。因此，由於在最表層經常存在吸附的氯離子的緣故，即使四級銨鹽聚合物吸附於析出銅面，由於四級銨鹽聚合物本身進入析出銅中的可能性低，具有不會降低析出銅純度的機能而較佳。The chloride ion in the sulfuric acid-based copper plating solution described above preferably has an organic additive in combination with the effect of adsorbing on the surface of the precipitated metallic copper and improving the uniformity of the surface state in the copper plating step. Then, by using a quaternary ammonium salt polymer and chloride ions in combination, chloride ions are adsorbed to copper, and an effect of suppressing copper adhesion to the copper surface is moderately suppressed. Therefore, in the case where a copper plating layer having a smooth surface is obtained, the control of chloride ions is often attempted. By allowing the quaternary ammonium salt polymer and the chloride ions to coexist in the solution, the chloride ions adsorbed on the surface of the copper foil move along the precipitation surface with a change in the surface potential, wherein the change in the surface potential is accompanied by Precipitation of copper particles. Therefore, since the adsorbed chloride ions are often present in the outermost layer, even if the quaternary ammonium salt polymer is adsorbed on the precipitated copper surface, the possibility that the quaternary ammonium salt polymer itself enters the precipitated copper is low, and the precipitation is not lowered. The function of copper purity is preferred.
藉由使用以上述的四級銨鹽聚合物與氯離子並存的硫酸系鍍銅液(燒鍍銅液)，即使是作為陰極的未處理銅箔的表面僅具備微米等級凹凸而無電流集中部位時，亦能夠更安定的在其表面均勻的析出細微銅粒子，且在同一面所析出的細微銅粒子並沒有偏移存在的情形。亦即是，以燒鍍銅條件析出形成的細微銅粒子的形狀、銅粒子尺寸的散亂小，且能夠安定的析出形成較佳的細微銅粒子。而且，上述的四級銨鹽聚合物雖然會吸附於銅上，但由於添加量為0.1mg/L～50mg/L就足夠的少量，因此在析出的細微銅粒子中混入的不純物少，對於所獲致之銅箔的導電性能不會產生不良影響。By using a sulfuric acid-based copper plating solution (baked copper liquid) in which the above-described quaternary ammonium salt polymer and chloride ions are present, even the surface of the untreated copper foil as the cathode has only micron-order irregularities and no current concentration portion. At the same time, it is possible to uniformly precipitate fine copper particles on the surface thereof, and the fine copper particles deposited on the same surface are not offset. In other words, the shape of the fine copper particles deposited by the copper plating conditions and the small size of the copper particles are small, and the fine copper particles can be formed by stable precipitation. Further, although the above-described quaternary ammonium salt polymer is adsorbed on copper, the amount of addition is preferably from 0.1 mg/L to 50 mg/L, so that the amount of impurities mixed in the precipitated fine copper particles is small. The conductive properties of the obtained copper foil do not adversely affect.
而且，對於上述的四級銨鹽聚合物與氯離子並存的硫酸系鍍銅液的組成進行更具體的描述。於本案發明的銅箔之粗化處理方法中，較佳使用銅濃度為5g/L～20g/L、硫酸濃度為50g/L～150g/L、四級銨鹽聚合物的濃度為0.1mg/L～50mg/L、氯離子濃度為1mg/L～100mg/L的硫酸系鍍銅液。Further, the composition of the sulfuric acid-based copper plating solution in which the above-described quaternary ammonium salt polymer and chloride ions coexist is more specifically described. In the copper foil roughening treatment method of the present invention, it is preferred to use a copper concentration of 5 g/L to 20 g/L, a sulfuric acid concentration of 50 g/L to 150 g/L, and a quaternary ammonium salt polymer concentration of 0.1 mg/ A sulfuric acid-based copper plating solution having a concentration of L to 50 mg/L and a chloride ion concentration of 1 mg/L to 100 mg/L.
此處銅濃度較佳為5g/L～20g/L的範圍。銅濃度即使低至5g/L以下，亦能夠在銅箔的表面析出形成細微銅粒子。但是電解電流密度如不變小的話，後續的第2鍍銅步驟無法得到良好的粒子形狀，生產性變差而較為不佳。而且，當該銅濃度低的話陰極電流效率降低，且所析出形成的細微銅粒子的尺寸或分佈發現散亂的傾向。另一方面，銅濃度超過20g/L的鍍銅液，電解電流密度不提高的話，則變成難以在未處理銅箔的表面析出形成細微銅粒子而較為不佳。The copper concentration here is preferably in the range of 5 g/L to 20 g/L. Even if the copper concentration is as low as 5 g/L or less, fine copper particles can be formed on the surface of the copper foil. However, if the electrolysis current density is not small, the subsequent second copper plating step cannot obtain a good particle shape, and the productivity is deteriorated and is not preferable. Further, when the copper concentration is low, the cathode current efficiency is lowered, and the size or distribution of the fine copper particles formed by the precipitation tends to be scattered. On the other hand, when the copper plating liquid having a copper concentration of more than 20 g/L does not increase the electrolytic current density, it is difficult to form fine copper particles on the surface of the untreated copper foil, which is not preferable.
然後，硫酸濃度較佳為50g/L～150g/L的範圍。此硫酸濃度位於上述範圍的話，由於電解電壓安定而不會產生電解電流的變動而較佳。另一方面，此硫酸濃度即使超過150g/L，對電解電壓的效果亦會減少，且由於管理成本亦會上昇而較為不佳。Then, the sulfuric acid concentration is preferably in the range of 50 g/L to 150 g/L. When the sulfuric acid concentration is in the above range, it is preferable that the electrolysis voltage is not stabilized and the electrolysis current is not changed. On the other hand, even if the sulfuric acid concentration exceeds 150 g/L, the effect on the electrolysis voltage is also reduced, and the management cost is also increased, which is not preferable.
而且，四級銨鹽聚合物的濃度較佳為0.1mg/L～50mg/L的範圍。此四級銨鹽聚合物的濃度未滿0.1mg/L的話，由於四級銨鹽聚合物的含量低，四級銨鹽聚合物無法在銅箔表面以必要充分的狀態吸附，無法得到細微銅粒子的均勻析出效果而較為不佳。另一方面，此四級銨鹽聚合物的濃度超過50mg/L的話，四級銨鹽聚合物的含量變為過剩，且四級銨鹽聚合物變為在銅箔表面的一部份過剩吸附的被覆狀態，在無法得到細微銅粒子的均勻析出效果的同時，析出的細微銅粒子中的雜質的混入量增加，而對所得銅箔的導電性能產生不良影響。Further, the concentration of the quaternary ammonium salt polymer is preferably in the range of 0.1 mg/L to 50 mg/L. When the concentration of the quaternary ammonium salt polymer is less than 0.1 mg/L, since the content of the quaternary ammonium salt polymer is low, the quaternary ammonium salt polymer cannot be adsorbed on the surface of the copper foil in a necessary sufficient state, and fine copper cannot be obtained. The uniform precipitation effect of the particles is less preferred. On the other hand, if the concentration of the quaternary ammonium salt polymer exceeds 50 mg/L, the content of the quaternary ammonium salt polymer becomes excessive, and the quaternary ammonium salt polymer becomes a part of excess adsorption on the surface of the copper foil. In the coated state, the uniform precipitation effect of the fine copper particles is not obtained, and the amount of impurities in the precipitated fine copper particles increases, which adversely affects the electrical conductivity of the obtained copper foil.
而且，氯離子濃度較佳為1mg/L～100mg/L的範圍。此氯離子的濃度未滿1mg/L時，難以得到氯離子均勻附著在於銅箔表面的狀態。其結果，即使上述四級銨鹽聚合物的濃度在最適當範圍，在使用四級銨鹽聚合物作為添加劑使用時，由於難以得到細微銅粒子的均勻析出效果因而較為不佳。另一方面，即使此氯離子濃度超過100mg/L，由於氯離子的添加效果飽和，反而會發現設備的腐蝕等不良影響而較為不佳。Further, the chloride ion concentration is preferably in the range of 1 mg/L to 100 mg/L. When the concentration of the chloride ion is less than 1 mg/L, it is difficult to obtain a state in which chlorine ions uniformly adhere to the surface of the copper foil. As a result, even when the concentration of the above-described quaternary ammonium salt polymer is in the most appropriate range, when a quaternary ammonium salt polymer is used as an additive, it is difficult to obtain a uniform precipitation effect of fine copper particles, which is disadvantageous. On the other hand, even if the chloride ion concentration exceeds 100 mg/L, since the effect of adding chlorine ions is saturated, adverse effects such as corrosion of equipment are found to be poor.
其次，描述本案發明的銅箔之粗化處理方法的電解條件。此步驟使用上述鍍銅液，在未處理銅箔的表面均勻的析出形成細微銅粒子。以下，於此粗化處理步驟以及後述的被覆鍍銅步驟中，對於銅箔作為陰極且對極搭配使用不溶性陽極時的電解條件進行說明。Next, the electrolysis conditions of the roughening treatment method of the copper foil of the present invention will be described. In this step, the above copper plating solution was used to uniformly precipitate fine copper particles on the surface of the untreated copper foil. Hereinafter, in the roughening treatment step and the coating copper plating step to be described later, the electrolytic conditions when the copper foil is used as the cathode and the insoluble anode is used in combination with the pole will be described.
首先，用於進行粗化處理的電解，較佳為使用液溫20℃～40℃的前述鍍銅液，採用平均陽極電流密度為5A/dm2 ～40A/dm2 的條件。首先進行關於液溫的描述。鍍銅液的液溫如未滿20℃，析出速度具有下降的傾向，析出銅粒子的形狀變得過小而較為不佳。另一方面，鍍銅液的液溫超過40℃的話，難以在上述銅濃度範圍得到燒鍍銅條件因而較為不佳。亦即是，採用液溫20℃～40℃的範圍會成為有利於工業生產上的範圍。First, the electrolysis used for the roughening treatment is preferably a copper plating solution having a liquid temperature of 20 ° C to 40 ° C, and a condition having an average anode current density of 5 A/dm 2 to 40 A/dm 2 . First, a description of the liquid temperature is performed. When the liquid temperature of the copper plating solution is less than 20 ° C, the precipitation rate tends to decrease, and the shape of the precipitated copper particles becomes too small and is not preferable. On the other hand, when the liquid temperature of the copper plating solution exceeds 40 ° C, it is difficult to obtain the conditions of the copper plating in the copper concentration range, which is not preferable. That is, the use of a liquid temperature range of 20 ° C to 40 ° C will be advantageous for industrial production.
其次，用以進行粗化處理的平均陽極電流密度較佳採用5A/dm2 ～40A/dm2 的條件。當此陰極電流密度未滿5A/dm2 時，呈現無法安定且均勻的析出形成細微的銅粒子的傾向。另一方面，當此陰極電流密度超過40A/dm2 時，所析出銅粒子的尺寸散亂變大而較為不佳。Next, the average anode current density for performing the roughening treatment is preferably 5 A/dm 2 to 40 A/dm 2 . When the cathode current density is less than 5 A/dm 2 , it tends to be unstable and uniformly precipitated to form fine copper particles. On the other hand, when the cathode current density exceeds 40 A/dm 2 , the size of the precipitated copper particles becomes larger and less preferable.
然後，用以進行粗化處理的燒鍍銅電解，較佳為分為2次以上的複數次來進行。這是因為此能夠減少進行燒鍍銅時容易發生的電流的集中部位的產生。作為此第2次以後的燒鍍銅電解條件，較佳是使用液溫20℃～40℃的前述鍍銅液，採用平均陽極電流密度為5A/dm2 ～40A/dm2 的條件。但是，此時對於最初的燒鍍銅之後的第2次以後的燒鍍銅，電流密度與進行最初的燒鍍銅的電流密度相較之下，較佳為小的電流密度。第2次以後的電流密度為最初的燒鍍銅條件以下的低電流密度的話，上述添加劑發揮平滑鍍銅的效果。其結果，最初析出的細微銅粒子之內，於小的銅粒子優先析出銅，而能夠得到銅粒子尺寸的水平化(leveling)效果。Then, the electroplating copper electrolysis for performing the roughening treatment is preferably carried out in plural times or more. This is because it is possible to reduce the occurrence of a concentrated portion of the current which is likely to occur when the copper is baked. As the second and subsequent hot-dip copper electrolysis conditions, the copper plating liquid having a liquid temperature of 20 to 40 ° C is preferably used, and the average anode current density is 5 A/dm 2 to 40 A/dm 2 . However, at this time, the current density of the second and subsequent calcined copper after the first copper plating is preferably a small current density as compared with the current density of the first calcined copper. When the current density after the second time is a low current density equal to or lower than the initial conditions of the copper plating, the additive exhibits the effect of smooth copper plating. As a result, in the fine copper particles deposited first, copper is preferentially precipitated in the small copper particles, and the leveling effect of the copper particle size can be obtained.
以上所述的用以進行粗化處理的燒鍍銅，1次或2次以上的電解的合計電解時間較佳為5秒～20秒的範圍。此合計電解時間未滿5秒時，有時於銅箔表面析出形成的細微銅粒子過小，而成為與未施加粗化處理的平滑面同等級的效果，進而成為無法對樹脂發揮錨效果的銅箔而較為不佳。另一方面，合計電解時間超過20秒的話，在銅箔表面析出形成的銅粒子粗大化，同一面內的部位的粗化處理等級的散亂大，而成為難以形成細微間距的配線電路的粗化處理而較為不佳。The total electrolysis time of the calcined copper used for the roughening treatment described above for one or two or more electroplating is preferably in the range of 5 seconds to 20 seconds. When the total electrolysis time is less than 5 seconds, the fine copper particles deposited on the surface of the copper foil may be too small, and may have the same effect as the smooth surface to which the roughening treatment is not applied, and further become a copper which cannot exhibit an anchor effect on the resin. Foil is not good. On the other hand, when the total electrolysis time is more than 20 seconds, the copper particles deposited on the surface of the copper foil are coarsened, and the level of the roughening treatment in the same plane is large, and the wiring circuit having a fine pitch is difficult to be formed. It is not good for processing.
除了以上所述的粗化處理之外，較佳亦可以使用硫酸系鍍銅液，對於析出形成有細微銅粒子的銅箔表面，以平滑鍍銅條件形成「被覆鍍銅層」。為了使藉由前述粗化處理而析出形成於銅箔表面的細微銅粒子的附著狀態安定化，而在細微銅粒子與銅箔的表面連續披覆銅層以整飾細微銅粒子的形狀，同時亦能夠防止細微銅粒子的脫落。In addition to the above-described roughening treatment, it is preferable to use a sulfuric acid-based copper plating solution to form a "coated copper plating layer" on the surface of the copper foil on which the fine copper particles are formed by smooth copper plating. In order to stabilize the adhesion state of the fine copper particles deposited on the surface of the copper foil by the roughening treatment, the copper layer is continuously coated on the surface of the fine copper particles and the copper foil to refine the shape of the fine copper particles. It is also possible to prevent the peeling of fine copper particles.
形成此「被覆鍍銅層」時，較佳採用以下條件：以硫酸系鍍銅液(銅濃度：45g/l～100g/l、硫酸濃度：50g/l～150g/l)的液溫為20℃～60℃，平均陽極電流密度5A/dm2 ～30A/dm2 進行至少一次電解、合計的電解時間為5秒～60秒。此處所使用的硫酸系鍍銅液的組成範圍，以採用上述電流密度條件為前提，只要是不會在前述粗化處理析出形成的細微銅粒子上產生燒鍍銅即可，並不需有特別的限定。然後，被覆鍍銅所使用的硫酸系鍍銅液，並不需特別使用添加劑，但是如含有氯離子等的鹵素離子的話，有時能夠得到更均勻的被覆鍍銅層。而且，此被覆是以平滑鍍銅條件進行，亦可以分為複數回電解以進行。When the "coated copper plating layer" is formed, the following conditions are preferably employed: a liquid temperature of a sulfuric acid-based copper plating solution (copper concentration: 45 g/l to 100 g/l, sulfuric acid concentration: 50 g/l to 150 g/l) is 20 The average anode current density is 5 A/dm 2 to 30 A/dm 2 at ° C to 60 ° C, and at least one electrolysis is performed, and the total electrolysis time is 5 seconds to 60 seconds. The composition range of the sulfuric acid-based copper plating solution used herein is based on the above-described current density conditions, and it is not necessary to produce a copper-plated copper on the fine copper particles formed by the roughening treatment. Limited. Then, the sulfuric acid-based copper plating solution used for the copper plating is not particularly required to be used. However, if a halogen ion such as chloride ions is contained, a more uniform coated copper plating layer may be obtained. Further, the coating is carried out under the conditions of smooth copper plating, and may be carried out by dividing into multiple electrolysis.
此被覆鍍銅所使用的鍍銅液的溫度較佳為使用20℃～60℃。此鍍銅液的溫度未滿20℃的話，如使用上述鍍銅液組成，由於會成為硫酸濃度與銅濃度一起提高的設定的硫酸系鍍銅液，有時會析出硫酸銅的結晶而較為不佳。另一方面，鍍液的溫度超過60℃的話，由於蒸發的水量變多，會在短時間內產生濃度的變動而較為不佳。雖然即使產生此種濃度變動，對於被覆鍍膜的不良影響少，但是容易造成硫酸與銅的濃度上昇而析出硫酸銅結晶，因而較為不佳。The temperature of the copper plating solution used for the copper plating is preferably from 20 ° C to 60 ° C. When the temperature of the copper plating solution is less than 20 ° C, the composition of the copper plating solution is used, and the sulfuric acid-based copper plating solution which is set to increase the sulfuric acid concentration and the copper concentration may precipitate copper sulfate crystals. good. On the other hand, when the temperature of the plating solution exceeds 60 ° C, the amount of water evaporated increases, and the concentration fluctuation occurs in a short time, which is not preferable. Even if such a concentration fluctuation occurs, the adverse effect on the coating film is small, but the concentration of sulfuric acid and copper is likely to increase to precipitate copper sulfate crystals, which is not preferable.
於以上經由粗化處理所形成的細微銅粒的表面，較佳為進一步析出形成更細微的極細微銅粒子。此步驟為考量與作為層合對象的絕緣樹脂基材的接著性而亦可施行的步驟，屬於可任意進行的步驟。但是，如在施加有平滑鍍銅的被覆鍍銅層上析出形成有細微銅粒子的話，與絕緣樹脂基材的接觸面積變大。亦即是對於無法期待大的化學接著力的熱塑性樹脂能夠得到更加安定接著力的效果。The surface of the fine copper particles formed by the above roughening treatment is preferably further precipitated to form finer fine fine copper particles. This step is a step which can be carried out in consideration of the adhesion to the insulating resin substrate to be laminated, and is a step which can be carried out arbitrarily. However, when fine copper particles are deposited on the coated copper plating layer to which smooth copper plating is applied, the contact area with the insulating resin substrate becomes large. That is, it is possible to obtain a more stable adhesion force to a thermoplastic resin which cannot expect a large chemical adhesion force.
然後，在藉由粗化處理形成的細微銅粒的表面進一步析出形成更細微的極細微銅粒子的方法，有幾種的方法被考慮。此些方法中，對細微銅粒的表面進行極細微銅粒子的析出形成時，較佳是亦使用含有四級銨鹽聚合物的鍍銅液以析出形成極細微銅粒子。此種極細微銅粒子的形成，如使用含有四級銨鹽聚合物的鍍銅液，能夠得到極細微銅粒的粒徑一致、良好的粗化處理型態。Then, a method of forming finer fine fine copper particles by further precipitation on the surface of the fine copper particles formed by the roughening treatment is considered. In these methods, when the fine copper particles are precipitated on the surface of the fine copper particles, it is preferred to use a copper plating solution containing a quaternary ammonium salt polymer to precipitate fine micro copper particles. In the formation of such ultrafine copper particles, if a copper plating solution containing a quaternary ammonium salt polymer is used, it is possible to obtain a fine grain size of a very fine copper particle and a good roughening treatment state.
本案發明的印刷配線板用銅箔：本案發明的印刷配線板用銅箔，是使用前述的銅箔之粗化處理方法所獲致之表面處理銅箔而作為印刷配線板用銅箔使用。在使用上述粗化處理方法所獲致之表面處理銅箔之粗化處理面上，均勻的附著有細微且粒子尺寸一致的細微銅粒子。亦即是，與構成覆銅積層板或是印刷配線板的絕緣樹脂基材進行層合時，絕緣樹脂基材與表面處理銅箔的接著界面的表面積變廣，密著性提昇。因此，即使在印刷配線板的製造步驟中施加藥品處理等，亦不易從配線電路端面受到藥品的侵蝕。而且，藉由銅粒子為細微，容易形成細微間距的配線電路。In the copper foil for a printed wiring board of the present invention, the copper foil for a printed wiring board of the present invention is used as a copper foil for a printed wiring board by using the surface-treated copper foil obtained by the above-described copper foil roughening method. Fine copper particles having a fine particle size and uniformly adhered to the roughened surface of the surface-treated copper foil obtained by the above-described roughening treatment method. In other words, when the insulating resin substrate constituting the copper clad laminate or the printed wiring board is laminated, the surface area of the interface between the insulating resin substrate and the surface-treated copper foil is widened, and the adhesion is improved. Therefore, even if a chemical treatment or the like is applied in the manufacturing step of the printed wiring board, it is difficult to be corroded by the medicine from the end surface of the wiring circuit. Further, by the fact that the copper particles are fine, it is easy to form a wiring circuit having a fine pitch.
而且，此處所述的印刷配線板用銅箔，因應各種印刷配線板的用途，亦記載有包含在粗化處理面上適當的施加防鏽處理層、矽烷偶合劑處理等的印刷配線板用銅箔的概念。In addition, the copper foil for a printed wiring board described above is also used for a printed wiring board including a rust-preventing treatment layer, a decane coupling agent treatment, and the like, which are appropriately applied to the roughened surface in response to the use of various printed wiring boards. The concept of copper foil.
本案發明的覆銅積層板：本案發明的覆銅積層板，是將前述印刷配線板用銅箔與絕緣樹脂基材層合的覆銅積層板。如上所述，使用該印刷配線板用銅箔的覆銅積層板，不受絕緣樹脂基材的種類限制，容易形成細微間距的配線電路，且為耐藥品性以及耐表層遷移性優良的覆銅積層板。而且，與含有玻璃布等補強材料的絕緣樹脂基材層合的覆銅積層板，由於所形成的配線電路與補強材料的接觸部位少，因此變成能提供可製造耐導電性陽極細絲物(Conductive Anodic Filament,CAF)性優良的印刷配線板的覆銅積層板。The copper-clad laminate according to the present invention is a copper-clad laminate in which the copper foil for a printed wiring board is laminated with an insulating resin substrate. As described above, the copper-clad laminate using the copper foil for a printed wiring board is not limited by the type of the insulating resin substrate, and it is easy to form a wiring circuit having a fine pitch, and is copper-clad which is excellent in chemical resistance and surface layer migration resistance. Laminated board. Further, since the copper-clad laminate which is laminated with the insulating resin base material containing a reinforcing material such as glass cloth has a small contact portion between the wiring circuit and the reinforcing material, it is possible to provide an anode filament-like material capable of producing conductive resistance ( Conductive Anodic Filament, CAF) Copper-clad laminate with excellent printed wiring board.
而且，於本案發明的覆銅積層板中，較佳亦可以於前述絕緣樹脂基材使用液晶聚合物。如同前述，高頻對應的可撓式印刷配線板多使用一併具有耐彎折性良好、吸水率小的優點的液晶聚合物。亦即是，與本案發明的印刷電路板用銅箔層合的液晶聚合物基材由於高頻特性良好且吸水率亦小，而適於製造長期可靠度提昇的可撓式印刷配線板或TCP。Further, in the copper clad laminate of the present invention, it is preferable to use a liquid crystal polymer in the insulating resin substrate. As described above, the flexible printed wiring board corresponding to the high frequency has a liquid crystal polymer which is excellent in bending resistance and water absorption. In other words, the liquid crystal polymer substrate laminated with the copper foil for a printed circuit board of the present invention is suitable for manufacturing a flexible printed wiring board or TCP having improved long-term reliability because of high frequency characteristics and low water absorption. .
本案發明的印刷配線板：本案發明的印刷配線板是前述覆銅積層板經蝕刻加工等所獲致之印刷配線板。如同前述，當該印刷配線板即使形成細微間距的配線電路，實用上亦具備充分的接著強度，且耐藥品性、耐表層遷移性、耐CAF性優良。亦即是能夠提供對於長時間使用具備良好可靠度的印刷電路板。In the printed wiring board of the present invention, the printed wiring board of the present invention is a printed wiring board obtained by etching or the like of the copper-clad laminate. As described above, even if the printed wiring board is formed with a fine pitch wiring circuit, it has practically sufficient bonding strength, and is excellent in chemical resistance, surface layer migration resistance, and CAF resistance. That is, it is possible to provide a printed circuit board with good reliability for long-term use.
此實施例是在厚12μm的未處理電解銅箔的析出面(表面粗糙度：Rzjis=0.6μm)作成施加粗化處理、防鏽處理以及矽烷偶合劑處理的3種類的表面處理銅箔(試樣1～試樣3)。此處，進行細微銅粒的形成所使用的燒鍍銅電解。然後，進行被覆鍍銅。此燒鍍銅以及被覆鍍銅的各電解液組成如表1所示，電解條件如表2所示。In this example, three types of surface-treated copper foils were subjected to roughening treatment, rust-preventing treatment, and decane coupling agent treatment on a deposition surface (surface roughness: Rzjis = 0.6 μm) of an untreated electrolytic copper foil having a thickness of 12 μm. Sample 1 to sample 3). Here, the copper plating electrolysis used for formation of fine copper particles is performed. Then, the coated copper plating is performed. The composition of each of the copper-plated copper and the copper-coated copper was as shown in Table 1, and the electrolytic conditions are shown in Table 2.
然後，所獲致之表面處理銅箔評價「表面粗糙度(Rzjis)」、「以雷射法測定2次元表面積為6550μm2 的區域時的3次元表面積(A)μm2 與測定的2次元表面積的比[(A)/6500]的值所計算的表面積比(B)」。尚且，以下記載評價項目對應的評價方法。Then, the surface-treated copper foil obtained was evaluated for "surface roughness (Rzjis)" and "three-dimensional surface area (A) μm 2 and a measured 2-dimensional surface area when a region having a 2-dimensional surface area of 6550 μm 2 was measured by a laser method. Surface area ratio (B)" calculated from the value of [(A)/6500]. In addition, the evaluation method corresponding to the evaluation item is described below.
表面粗糙度(Rzjis)：表面處理銅箔的表面粗糙度(Rzjis)，是使用具備前端的曲率半徑r為2μm的鑽石尖筆的探針式表面粗糙計(小坂研究所股份有限公司製SE3500)，並以JIS B 0601為基準進行測定。其評價結果如後述表3所示。Surface roughness (Rzjis): The surface roughness (Rzjis) of the surface-treated copper foil is a probe type surface roughness meter using a diamond tip pen having a curvature radius r of 2 μm at the tip end (SE3500, manufactured by Otaru Research Co., Ltd.) And measured based on JIS B 0601. The evaluation results are shown in Table 3 below.
表面積比：表面處理銅箔的3次元表面積，是使用超深度彩色3D形狀測定顯微鏡(股份有限公司KEYENCE製VK-9500，使用雷射：可視光界限波長408nm的紫外光雷射)，對2次元表面積為6550μm2 的區域進行測定，計算表面積比。其評價結果如後述表3所示。Surface area ratio: The 3-dimensional surface area of the surface-treated copper foil is an ultra-deep color 3D shape measuring microscope (VK-9500 manufactured by KEYENCE Co., Ltd., using a laser: ultraviolet light with a visible light limit wavelength of 408 nm), for a 2-dimensional The area having a surface area of 6550 μm 2 was measured, and the surface area ratio was calculated. The evaluation results are shown in Table 3 below.
粗化處理面外觀：使用本案發明的粗化處理方法而表面粗化的電解銅箔(試樣1)，其掃描式電子顯微鏡(SEM)像如圖1所示。Appearance of roughened surface: An electrolytic copper foil (sample 1) having a surface roughened by the roughening treatment method of the present invention, and a scanning electron microscope (SEM) image thereof is shown in Fig. 1 .
剝離強度：於此實施例所獲致之試樣1～試樣3的粗化處理面，製造施加有防鏽處理以及矽烷偶合劑處理的表面處理銅箔。然後此表面處理銅箔與市售的液晶聚合物基材重合，使用真空加壓機，加壓加熱成形而作成片面覆銅積層板。其後，在對該片面覆銅積層板的銅箔面進行面整理後，全面的積層乾膜。於此乾膜上搭載用以形成評價用配線電路形狀的罩幕膜並進行曝光、顯影，將未曝光部分的乾膜去除以形成抗蝕層。其次，利用氯化銅(CuCl2 )蝕刻液以蝕刻未被抗蝕層被覆部分的銅箔。進一步，將抗蝕層剝離，得到具備密著性評價用的寬10mm的直線狀的剝離強度測定用電路的試驗片。上述試驗片的剝離強度，使用萬能試驗機、以JIS C 6481為基準進行測定。其評價結果表示於下述表3。Peel strength: The surface-treated copper foil to which the rust-preventing treatment and the decane coupling agent treatment were applied was performed on the roughened surfaces of Samples 1 to 3 obtained in the examples. Then, the surface-treated copper foil was superposed on a commercially available liquid crystal polymer substrate, and formed into a sheet-faced copper-clad laminate by pressurization and heating using a vacuum press. Thereafter, after the surface of the copper foil of the one-side copper-clad laminate is surface-finished, a dry film is laminated in a comprehensive manner. A mask film for forming a shape of the evaluation wiring circuit is mounted on the dry film, exposed and developed, and the dry film of the unexposed portion is removed to form a resist layer. Next, a copper chloride (CuCl 2 ) etching solution is used to etch a copper foil which is not covered by the resist layer. Further, the resist layer was peeled off to obtain a test piece having a linear peel strength measuring circuit having a width of 10 mm for adhesion evaluation. The peeling strength of the above test piece was measured using a universal testing machine based on JIS C 6481. The evaluation results are shown in Table 3 below.
依實施例得到的表面處理銅箔的細微銅粒子，儘管以燒鍍銅條件電解，如同由圖1所能夠理解的，能夠形成無異常析出且平坦的粗化處理表面。而且如同由表3所能夠理解的，由作為表面處理銅箔的表面粗糙度來看，能夠形成可形成細微間距電路等級的低輪廓化、細微且均勻的粗化處理表面。The fine copper particles of the surface-treated copper foil obtained in the examples were electrolyzed under the conditions of the copper plating, and as can be understood from FIG. 1, it was possible to form a roughened surface which was free from abnormal precipitation and flat. Further, as can be understood from Table 3, from the viewpoint of the surface roughness of the surface-treated copper foil, it is possible to form a low-contour, fine and uniform roughened surface which can form a fine pitch circuit level.
再者，由表3所能夠理解的，證實了本案發明的表面處理銅箔之粗化處理即使為低輪廓化，由於其表面積比高，而能夠得到0.8kgf/cm以上的良好剝離強度。Further, as can be understood from Table 3, it was confirmed that the roughening treatment of the surface-treated copper foil of the present invention can achieve a good peeling strength of 0.8 kgf/cm or more because of its high surface area ratio even if it is low profile.
本案發明的銅箔之粗化處理方法，為適用於印刷配線板用銅箔的與絕緣樹脂基材的層合面的粗化的方法。依此方法而經粗化處理的銅箔，顯示了與低介電常數的絕緣樹脂基材的良好密著性，而成為適於形成細微間距的配線電路的粗化處理面。特別是此細微銅粒子與防鏽處理進行適當組合的話，即使是與缺乏與銅箔密著性的熱塑性樹脂的密著亦良好，因此容易製造使用有具備低介電損失特性的絕緣樹脂基材的覆銅積層板。而且，由於銅箔之粗化處理是以細微且均勻的細微銅粒子進行，因而容易提供具備細微間距的配線電路的對應高頻的印刷配線板。The method for roughening the copper foil according to the present invention is a method for applying a roughening of a laminated surface of an insulating resin substrate to a copper foil for a printed wiring board. The copper foil which has been subjected to the roughening treatment according to this method exhibits good adhesion to the insulating resin substrate having a low dielectric constant, and becomes a roughened surface suitable for forming a wiring circuit having a fine pitch. In particular, when the fine copper particles are appropriately combined with the rust-preventing treatment, the adhesion to the thermoplastic resin lacking the adhesion to the copper foil is good, so that it is easy to manufacture and use an insulating resin substrate having low dielectric loss characteristics. Copper clad laminate. Further, since the roughening treatment of the copper foil is performed by fine and uniform fine copper particles, it is easy to provide a high-frequency printed wiring board having a fine pitch wiring circuit.
圖1所示為試樣1的處理面的SEM觀察像。Fig. 1 shows an SEM observation image of the treated surface of the sample 1.
Claims (6)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008140180 | 2008-05-28 |
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| TW201009130A TW201009130A (en) | 2010-03-01 |
| TWI434965B true TWI434965B (en) | 2014-04-21 |
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| TW098117407A TWI434965B (en) | 2008-05-28 | 2009-05-26 | A roughening method for copper foil, and a copper foil for a printed wiring board which is obtained by the roughening method |
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| Country | Link |
|---|---|
| US (1) | US20110127074A1 (en) |
| JP (1) | JP5524833B2 (en) |
| KR (1) | KR20110014215A (en) |
| CN (1) | CN102046853B (en) |
| MY (1) | MY150495A (en) |
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| WO (1) | WO2009145207A1 (en) |
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- 2009-05-26 TW TW098117407A patent/TWI434965B/en not_active IP Right Cessation
- 2009-05-27 US US12/994,559 patent/US20110127074A1/en not_active Abandoned
- 2009-05-27 MY MYPI20105515 patent/MY150495A/en unknown
- 2009-05-27 JP JP2010514502A patent/JP5524833B2/en not_active Expired - Fee Related
- 2009-05-27 WO PCT/JP2009/059651 patent/WO2009145207A1/en active Application Filing
- 2009-05-27 CN CN200980119517XA patent/CN102046853B/en active Active
- 2009-05-27 KR KR1020107028700A patent/KR20110014215A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| CN102046853B (en) | 2013-05-15 |
| CN102046853A (en) | 2011-05-04 |
| WO2009145207A1 (en) | 2009-12-03 |
| MY150495A (en) | 2014-01-30 |
| US20110127074A1 (en) | 2011-06-02 |
| JP5524833B2 (en) | 2014-06-18 |
| JPWO2009145207A1 (en) | 2011-10-13 |
| KR20110014215A (en) | 2011-02-10 |
| TW201009130A (en) | 2010-03-01 |
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